201132788 六、發明說明： 【發明所屬之技術領域】 本發明係關於薄膜澱積技術，尤其關於藉於一澱積表面形成 澱積物及利用化學品處理該澱積物而形成導電性吸光氧化薄膜 之一種方法，以及關於使用該方法所形成之導電性吸光氧化膜。 【先前技術】 原子層澱積（ALD)法為澱積均勻厚度的薄膜於各種形狀，甚 至複雜的三維（3D)構造等基體（substrate)上所用之習知方法。在 ALD法中，被覆（塗）層（coating)係藉先驅物質與被覆表面間的表 面反應的交替反覆，尤其是自限表面反應形成。因此，ALD法 之形成機制可使塗層大致不具方向效應。 在ALD法中係將二或更多的化學品（即先驅物質）以依序、 交替方式引入反應室中使該化學品吸附於基體等表面上。此種化 學品的依序、交替引入通常稱為化學品的衝給（pulsing)或配給 (dosing)。在每次化學品的衝給之間通常有一沖淨（purging)期， 在此期間不與在該方法中所用之化學品相反應之氣體流乃通過 反應室引入。此氣體通常被稱為載送氣體（carrier gas)或沖淨用 氣體（purge gas)，對所用之化學品係呈惰性（inert)。使用此氣體 沖淨反應室内之剩餘化學品及由基體表面與化學品間相反應所 生成之副產物。此種沖淨亦可利用其他手段實現，同時澱積法亦 可用例如ALE (原子層磊晶術）、ALCVD (原子晶化學蒸鍍法）、 循環蒸鍍法等其他方法。這些方法的主要特徵為使澱積表靣依次 曝露於先驅物質以及該澱積表面上之先驅物質的成長反應e薄膜 可藉反覆數次實行衝給程序，利用ALD法使其成長。此衝給程 201132788 序包括上述之含有先驅物質之衝給（pulses)及沖淨期。此程序之 實行次數稱為“ALD循環”，其反覆次數乃由目標之膜厚或被 覆層厚度決定。 適合用以實行上述ALD法或類似ALD法已例如揭露於美國 專利6824816號（揭露用ALD法澱積貴金屬薄膜）及美國專利 6174377號及4389973號（揭露ALD法所用之澱積裝置）。關於 ALD法的一般基礎概要則可參照“原子層磊晶術” ^書 (Suntola 等人著，Blackie and Son 公司，1990 出版）。 先前技術揭露在ALD法或其類似方法中用以藉交替曝露 基體表面於不同化學品在基體上合成及澱積薄膜之廣範圍材 料。但導電性暗色光吸收氧化膜則未見使用ALD法製造。例如，201132788 VI. Description of the Invention: Technical Field of the Invention The present invention relates to a thin film deposition technique, and more particularly to forming a conductive light absorbing oxide film by forming a deposit on a deposition surface and treating the deposit with a chemical. One method, and a conductive light absorbing oxide film formed using the method. [Prior Art] The atomic layer deposition (ALD) method is a conventional method for depositing a film of uniform thickness on various shapes, even a complex three-dimensional (3D) structure. In the ALD method, the coating is formed by an alternating reaction of the surface reaction between the precursor material and the surface of the coating, especially a self-limiting surface reaction. Therefore, the formation mechanism of the ALD method allows the coating to have substantially no directional effect. In the ALD method, two or more chemicals (i.e., precursor substances) are introduced into the reaction chamber in a sequential or alternating manner to adsorb the chemical on the surface of the substrate or the like. This chemical is introduced sequentially or alternately into the pulsing or dosing of what is commonly referred to as a chemical. There is usually a purging period between each chemical flush, during which a gas stream that does not react with the chemicals used in the process is introduced through the reaction chamber. This gas is commonly referred to as a carrier gas or a purge gas and is inert to the chemicals used. This gas is used to flush the remaining chemicals in the reaction chamber and by-products formed by the reaction between the substrate surface and the chemical phase. Such flushing can also be achieved by other means, and other methods such as ALE (atomic layer epitaxy), ALCVD (atomic chemical vapor deposition), and cyclic evaporation can be used for the deposition method. The main feature of these methods is that the deposited surface is exposed to the precursor material and the growth reaction e film of the precursor material on the deposition surface can be subjected to a rushing process several times, and grown by the ALD method. This rush gives the process 201132788 sequence including the above-mentioned pulse and flush period of the precursor material. The number of times this program is executed is called the "ALD cycle", and the number of times of repetition is determined by the film thickness of the target or the thickness of the coating. Suitable for carrying out the above-described ALD method or similar ALD method, for example, is disclosed in U.S. Patent No. 6,824,816 (Preparation of a noble metal film by ALD) and U.S. Patent Nos. 6,174,377 and 4,389,973 (disclosure devices for use in the ALD process). A general summary of the ALD method can be found in the book "Atomic Layer Deposition" (Suntola et al., Blackie and Son, 1990). The prior art discloses a wide range of materials for synthesizing and depositing a film on a substrate by alternately exposing the surface of the substrate to different chemicals in the ALD process or the like. However, the conductive dark light absorbing oxide film was not produced by the ALD method. E.g,
ZnO : AI及In2〇3 : Sn等透明導電氧化物(TC〇)以前是用ALD法 殿積。但即使這些氧化膜為導電性，其在可視波長範圍内大致呈 透明。 在美國專利7270895號有揭露一種具有暗色被覆層的物 肢’其所揭露之形成被覆層的方法為陰極弧蒸鍍法（CAE)、噴鍍 法及PVD法。這些被覆法的共同問題為對於複雜形狀的基體及 非平坦表面無法達成均勻塗覆。此在裝飾性應用上尤為成問題， 因為其所要求的塗覆層為能均勻被覆基體的整個表面。 氧化絡(〇2〇3)為一般所熟知之可表現暗灰色調的材料。此 ，料已廣被使用，而此氧化鉻的澱積法揭露於美國專利7147794 號中澱積氧化鉻的方法在複雜形狀的三維（3D)物體等非平坦表 上…、去形成均勻厚度的被覆膜。同時鉻及氧化絡材料又進一梦 具有關引起鉻過敏症的問題。 201132788 一種高吸收性，即暗色且又導電性的 二維（3D)物體的非平坦表面上形成 本發明人等鏗於有需要 薄膜材料及可在各種形狀的 厚度均勻的被覆層的方法。 【發明内容】 本發明之目的乃在解決上述習知技術之問題’提供一種在基 表面开^/成導电性氧化膜的新方法以及提供新型之導電性氧化 膜及其用途。 本發明之方法的特徵界定於申請專利範圍請求項丨中；本發 月之產即導電性氧化膜，界定於請求項19中而該氧化膜之 用途界定於請求項26及27中。 在基體表面形成導電性氧化膜的本發明方法包括下述步驟： 將基體置於反應t中；在該基體的殿積表面（depose surface)形成初步鍍層（dep〇sh);及使用化學品（先驅物質理 該澱積鍍層表面。. 上述之在基體表面殿積初步鍍層的步驟包括： 除’即沖淨反應室 在該澱積表面形成過渡金屬氧化物之初步鍍層；隨後噴吹清 使用化學品處理殿積鍛層表面之步驟包括： 以有機金屬化學品處理該鍍層表面，而該有機金屬化學品含 有第一金屬使該有機化學品之至少一部分可與該初步鍍:反 應，隨後噴吹清除反應室以形成含有氧、第一金屬及過渡金^之 氧化物；上述之形成初步鍍層及處理該鍍覆表面之步驟係交替爻 覆貫行使在該基體表面形成導電性氧化物薄獏（即氧化膜）。 本發明之導電性氧化物包含氧、第—金屬及過渡金屬、。該氧 201132788 化膜係藉在基體之澱積（鍍層）表面上形成過渡金屬氧化物之初 步鍍層（preliminary deposit)，隨後噴吹清除反應室，進而用含有 第一金屬之有機金屬化學品處理該澱積表面使該有機化學品之 至少一部分與該初步鍵層的至少一部分反應，然後噴吹清除該反 應室以形成含有氧、第一金屬及過渡金屬之氧化物。此種形成初 步鍍層及處理澱積表面之步驟係交替反覆實施，直至在基體上形 成導電性氧化膜。 在此應注意，本文中所用“導電性”一詞係指薄膜為電非絕 緣性，即除非另有註明，該詞係包含半導電性及導電性薄膜。 另外，“澱積（deposit)” 一詞係指極微量之材料㈦以打⑷）， 例如厚度低於數單原子層（m〇n〇hyers)之鍍層，其中原子可能不 組入成一特定的相（phase)而使本發明的優點可發揮。經已發現只 在形成初步澱積的步驟及使用有機化學品處理澱積表面之步驟 又替反覆:T行使導電性氧化顧彡成於基體表面，始能使此材料被 膜具備有益的性能。基於此理由，“薄膜（film)，，一詞庫解作一 Π = 材料量足夠讓薄膜中的原子組入於相中從而具備 及“ = 提的是文中之步驟“形成初步_” 宜兩定要連續實行，而依本發明係可在 之間3 —些其他步驟。此等其他步驟可例如包括··令1他 應不完it面成長殿積，使該初步殿積與有機金屬化學品i反 行，ί在m刀合步=積^里誠積表面的步驟係交替的實 3月頌的重疊。此乃意味在同一反應室中不會 201132788 =時有大量之初錢積成長所有之化學品及處理該殿積表面所 =之化干品（有機金屬化學品）存在1此，初麵積之形成程 不會明顯的影響澱積表面之處理程序，相反亦然，但精於此項 祕之人可依本說明書之揭露内容知曉，當上述二步驟例如在同 一，應室中實行時，紐步驟之殘餘化學品可長時間留存於該反 應室中，而此殘餘物可能某程度的影響繼後之處理步驟，即該二 步驟在時間上列顯重疊。於是，交替實行該二步 = :控管形，化膜之化學反應主要發生在殿積表面上= 处—而非遠n殿積表面之氣相（gasphase)内。除非另有註明， 此定義亦仙於本說明書中討論之擬交㈣行之其他處理步驟。 依本發明之第—實施例，其過渡金屬氧化物的初步殿積包括 ，何順序之以下的交替步驟：a)曝露基體之澱積表面於含氧化學 时/吏4含氧化學品之至少一部分被吸附於該澱積表面上，隨後 沖淨反應室；b)曝露基體之澱積表面於過渡金屬化學品的至少一 分被吸附於該澱積表面上，隨後沖淨反應室。 依本發明之第二實施例，其使用有機金屬化學品處理澱積表 面之步驟包括：c)曝露基體之澱積表面於有機金屬化學品，使該 有機金屬化學品的至少一部分被吸附於該澱積表面上，隨^ 反應室。 净 又，依本發明之一實施例，本發明之方法在基體上形成導電 性氧化獏，用以吸收光線。依另一實施例之本發明方法為用以在 基體上形成導電性氡化膜，以衰減電磁波在該導電性氧化膜中 傳播於可視波長範圍内。 、之 依本發明之一實施例，導電性氧化膜係作為基體的被覆犋， 201132788 用以吸收光線，而依另一實施例則作為基體的導電性膜，以衰減 電磁波在該導電性氧化膜中之傳播於可視波長範圍。 “可視波長範圍” 一詞，除非另有註明，係如同人可看見波 長帶(wavelength band) ’即指電磁波譜之侧〜75〇奈米（nm)波長 帶0 膜 依本發明之-實施例之方法係包括形成導電性吸光氧化啦 π此方法包含形成-種高損耗膜(1〇ssy fUm)。另外，依本發甲 方法’即使立體(3D)物體表面為複雜的非平坦面亦可形成極為_ 致的被覆膜❺上述之外，本發明方法有助於例如使用此被覆糖 作光學設言卜被覆膜的材料具有良好的化學安定性，即例如將发 曝露於大氣條件或其他潛在性氧化條件下（此時膜體可能曝露於 濕亂，/或氧）時表現良好之安定性。又，本發明方法能製造導 電性氧化膜而此方法能夠正確的控制該薄膜的導電性。形成薄膜 的材料亦驚奇的具有高吸光係數，有些材料在電磁光譜之可視部 分具有相當均勻之吸收波譜(abs〇rpti〇n啊㈣。 Μ办能Ϊ產生^述利益之本發明方法的理論根據，可認為是：當 2金屬氧化物之初㈣積物與有機金屬 ，學品的第一金屬即組入該嶋中作為其一部有: 光學吸收性導電氧化物。有關 7成 (包含氣、i5、、…”收性及導電性氧化物 之可視光且卿朗氧化物·; 相提供具有高吸收係數 此種導電性氧化膜（即氧化物的導電膜）可藉交替 初步殿積物及處理該_物的步驟而形成。此導電性氧化物2 8 201132788 優點。另外，上面所述步驟的反覆實行導致至少部分 ^相心◊制使該導電性氧化膜的有利保形性—ality)具 有相當均勻厚度的形貌(profile)。 ^行本發明之有些實施例的步驟心)及c)的順序有許多不 而有些實施例則有特定的順序。即有些實施例a)及咐 蚀i通實行m彡成初步澱㈣在㈣e)巾將該初步殿 '』、路於有機金屬化學品。本發明不限制步驟e)之前的步驟 a)及b)的反覆次數。 依本發明的一實施例步驟a)、b)及c)係依a)、b)、c)然後 的順序’而依此順序反覆實行—或多次增加膜厚。又有一 f ^彳丨V驟a)、^*)及c)係依a)、b)、c)的順序而將此順序反覆 貫行一或多次以增加膜厚。更有__實施例，步驟a)、b)及c)係依 a)及b)而將此依步驟反覆實行一或數次後再實行步驟幻。 由於每次將基體的表面曝露於化學品時會使該化學品的一 部为吸附於該基體的表面，因此在本發明之某些實施例中可藉基 體表面曝露於化學品之次數來控制澱積膜的厚度。此種在基體上 形成薄膜的方法可非常正確的控制薄膜的厚度，因此薄膜中之總 吸光度，亦即薄膜的暗度，可正確的控制。當担任薄膜成長之化 學品交替存在於反應室内時，該化學品即不能夠充份的混合，而 问度吸收性薄膜（highly absorbing film)的形成主由澱積表面之吸 附反應所控制。這些吸附反應之動力學則主由澱積面的性質控 制，較不太受在反應室内之澱積表面之化學品的流動力學之影 響。但在本發明之有些實施例中，則引致在任何形狀之基體的澱 積表面形成極為保形（conformal)且均勻厚度之高度吸收性薄膜。 201132788 依本發明之一實施例，步驟a)、b)及c)係各實行一或數次， 用以在基體上形成厚度lnm至2μηι之薄膜。當膜厚在lnm以下 或2μπι以上時，該薄膜分別在目視上呈透明及不透明。因此厚 度在上述lnm至2μιη間之薄膜可有效的作為灰度濾光片使用。 依本發明之一實施例，反應室内之壓力在基體表面曝露於化 學品時是保持在0.1耗巴（O.lhpa)及100耗巴（lOOhpa)之間。依另 一實施例，基體表面溫度為150°C〜600°C範圍，較好為200°C〜500 °C範圍，最好為250°C〜450°C範圍。 依本發明之一實施例.，過渡金屬化學品為過渡金屬il化物。 依另一實施例，過渡金屬鹵化物為過渡金屬氯化物，又依再一實 施例，該過渡金屬氣化物為選自下列群中，三氣化鈦、四氣化鈦、 四氣化錯、四氣化铪、五氣化銳、五氣化組、五氣化翻及六氣化 鶴。 依本發明之另一實施例，該過渡金屬化學品為含有過渡金屬 之乙醇化合物。 依本發明之實施例，有機金屬化學品之金屬部份係選自下列 群中，鋁、鎵及過渡金屬。依本發明之一實施例，有機金屬化學 品之有機部份則含有烷基配合基（alkyl ligand)，又依另一實施 例，有機金屬化學品為三曱基鋁。 依本發明之一實施例，含氧化學品亦含有氫。另一實施例之 含氧化學品為水。依其他實施例，含氧化學品為臭氧、氧離子、 氧、乙氧基金屬、H202及N2〇。 藉適當的選用化學品及處理加工參數，特別是基體表面曝露 於化學品時的基體溫度及反應室内的壓力、可以使吸附化學品於 10 201132788 澱積表面、過渡金屬氧化物之初步澱積及使用有機金屬化學品處 理此初步澱積物之動作成為自限方式（self-limiting)。此可進一步 改進形成薄膜厚度之均句性及具有複雜外形之立體物體表面之 吻合性（conformality)。加之，上面所列化學品均不貴且本發明方 法可低成本的實行。 依本發明之一實施例，基體為非平面。 又，依本發明之實施例，薄膜宜含有40〜80原子％範圍之 氧，較佳為55〜75原子％，最佳為60〜70原子％範圍。依本發明 之另一實施例，薄膜宜含有5〜40原子％範圍之第一金屬，較好 為7〜30原子。/〇,最好為10〜25原子％範圍。另外，依本發明之 又一實施例，薄膜宜含6〜30原子％之過渡金屬，較好為10〜25 原子°/。，最好為13〜23原子％範圍。本發明之薄膜含有氧、過渡 金屬及第一金屬，且氧的原子與過渡金屬的原子％及第一金屬的 原子％之和的比率係在1.8〜2.1之範圍。本發明之利點由上面所 述之組成範圍更加突顯。 依本發明之一實施例，第一金屬為鋁，而依另一實施例過渡 金屬為鈦。 依本發明之一實施例，含氧化學品為水，過渡金屬化學品為 四氯化鈦而有機金屬化學品為為三曱基I呂。 依本發明之一實施例，基體為在電磁光譜之可視部分呈大致 透明。依另一實施例，基體為透鏡。在眼鏡等之透鏡上可使用本 發明之薄膜，使其一邊具特殊的顏色外表一邊減衰此顏色外表 (color appearance)以保持自然之視覺效果。 上面所述的本發明實施例可以任何組合供使用。可將數個實 11 201132788 施態樣組合形成另-實施例。又，本發明之方法、產物或用途可 含上述本發明實施例之至少一個。 一 【實施方式】 爰參照附圖說明本發明之若干實施態樣於下。 α下㈣露本發明之若干實施例’精於此項技術之人可 根據揭露内容應用實施’故未對實施例之所有步驟作詳細的說 明。 舉例而言’適合用以實施本發明之下述實施例方法之加工裝 置的構造為精於此項技術之人根據本說明書之揭露得以知曉。該 裝置可為例如傳統上適合處理下述化學品所用之ALD (原子層 澱積）裝置。ALD裝置（即反應器）已揭露於美國專利第4389973 號及4413022號，這些文獻併入本案供作參考。有關操作此步 驟，，例如導入基體於反應家中，抽排反應室至低壓或若是該處理 (製)仏在大氣壓下實行時則調節流入裝置内之氣體流量，以 及加熱基體及反應室等，這些均為精於此項技術之人可根據本說 明書顯而易知者。另外，為了突顯本發明各種實施例之相關特 徵，對於許多其他操作及特點未予詳述或提到。 在本說明書中’除非有特別說明，“基體表面”、“表面” 及澱積表面’，等名詞係用以指基體的表面或在基體上已形成 之薄膜的表面。因為澱積表面在基體的表面吸附化學品而形成薄 膜的方法期間發生變化。 下述之本發明實施例係由將基體放置於例如實施ALd法適 用之典型反應裝置之反應室中開始（步驟丨），該反應室隨後用 真空系等抽排(pump down)至適合形成薄膜之壓力，或如為使用 12 201132788 大氣壓ALD裝置及/或方法時，則通常設置氣流從大氣保護澱積 區（deposition zone)。基體可例如通過氣密式載鎖裝置或單純的 通過裝載閘門（loading hatch)導入反應室内。基體可用電阻加熱 元件等加熱，此加熱涉及整體反應室。上述步驟1)亦可包括例 如在基體上成長薄膜或準備基體供繼下處理步驟等其他準備程 序。此準備程序可依反應裝置或該反應裝置之操作環境而決定。 此種程序之實施為精於此項技術之人依本說明書顯而易知。 在基體及反應室到達所定溫度及適合澱積之條件後，開始使 澱積表面交替曝露於不同之化學品以形成過渡金屬氧化物之初 步澱積。此種初步澱積在本發明之其他實施例中可藉例如CVD 或PVD等不用交替的將澱積表面曝露於不同化學品之方法形 成。 基體的表面宜曝露於氣態之化學品。即首先將化學品分別置 於容器中，視化學品性質加熱或不加熱，使其汽化，然後通過反 應裝置之管道將該汽化之化學品定量引入反應室中。此定量引入 汽化之化學品可藉裝設於管道之閥門實施，此閥門在適合ALD 裝置中通稱為脈動閥（pulsing valve)。可使基體在反應室内與化 學品接觸之其他機構亦可想到，其一為使基體表面在反應室内移 動（以替代汽化化學品移動），即使基體通過由汽態化學品所佔 據之區域。 典型之ALD反應器亦含有在引導另一化學品進入反應室前 使氮及氫等載體氣體進入反應室中沖淨剩餘之化學品及反應副 產物之設施。此一特徵連同汽化化學品之控制的定量引入可使基 體表面交替的曝露於化學品，免除在反應室内及ALD反應器的 13 201132788 其他部分過度拌合不同之化學品。在實施上，載送氣體㈣心 gas)通常在澱積程序期間係連續的通過反應室流動而另有各種 化學品隨同載送氣體交替的被引人反應室中。反應室之沖淨 (purgmg)並無需將剩餘的化學品及反應副產物從反應室完全清 除，常允許有這些或其他材料之殘餘物存在。 在上面討論的製程步驟U後，依本發明第-實施例（如圖！ 所不）為實行步驟a)，即將基體的表面曝露於含氧化學品。在此 種處理後，在上面討論之適宜處理條件下，可在該表面吸附部分 的a氧化子ac^在沖淨反應室後，將該表面曝露於過渡金屬化學 品（步驟b))，此時該過渡金屬化學品的一部分可被由步驟^形成 =面吸附。在步驟a)後之步驟b)則在殿積表面形成過渡金屬 氧化物之初步殿積物。在步驟b)之沖淨步驟後，將該形成之表 面曝露於有機金屬化學品（步驟c))，即用有機金屬化學品處理該 初步殺積物。經此處理後可使—部分之#機金屬化學品吸附於該 2表面々果可使該有機金屬化學品中之第—金屬组入該殿積 。iW後冲淨反應室。如上面所述，每—曝露步驟a)、匕)或 0可在_表面形成附加澱積物作為對應化學品及殿積表面之 吸附反應的結果。基體上线積物的厚度可藉反覆依序實行步驟 a)、b)及c)使其增加，如圖丨流程圖所示。 ，足夠厚度之澱積物時’該澱積物即形成由氧、來自有 膜、：=品之第一金屬及過渡金屬之氧化物材料構成之薄 =種導電性氧化物材料的薄膜具有多種上面說明之有利性 2待達到目標的膜厚後’停止交替曝露處理，而加工程序即告 終結。 14 201132788 依本發明之第2實施例，步驟a)，為將基體的表面曝露於含 氧=學品，如圓2所示。在下面所述之適當處理條件下，將表面 曝路於s氧化學品時舍使含氧化學品部分的吸附於基體表面。在 反應至沖淨之後，將該表面曝露於過渡金屬化學品（步驟b))，而 此過渡金屬化學品的一部分乃被吸附於由步驟&)形成之表面 上。在步驟a)可在澱積表面形成過渡金屬氧化物之初步澱積物。 ^步驟b)之沖淨處理後，將形成之表面曝露於有機金屬化學品 :))卩用有機金屬化學品處理該初步殿積物。此處理可在 該=表面吸附該有機金屬化學品之一部分；結果使該有機金屬 化學品中之第一金屬組入於該澱積物中。隨後沖淨反應室，繼之 使該生成之表面再度曝露於過渡金屬化學品，隨後沖淨反應室， 即重覆步驟b)。如上所述’作為對應化學品與澱積表面之吸附 ^應結果，每—曝露㈣a)、_ e)可在表面形成附加的殿積 。在基體上之殿積物的厚度可藉圖2所示之順序反覆步鄉a)、 b)^c)及b)使其增加。當澱積物到達足夠的厚度，該殿積物即形 2有氧、來自有機金屬化學品之第—金屬及過渡金屬之氧化物 ^科薄膜。_導電性氧化膜具有上面所討論之？财利性質。 在目標膜厚到達時停止交替曝露而終結製程。 衡2 實施射，曝露步驟之最短反覆程序稱為“脈 ^r^(p lsingsew ;ffl 二b)、c)，而圖2之第二實施例的脈衝程序a)、贼 =於化學品係可依製程的每—曝露步驟使用不同化學品。例如 &圖/之第-實_，其步驟a)之含氧化學品可依每次脈衝程序 b)、e)之反覆改變。此亦適用於其他實施例。 15 201132788 上述方法在一個澱積循環可能無法提供一完整的單層澱積 膜。在每一次澱積循環之後，澱積表面具有許多開放成核位址 (open micleation sites)。一個完整的單層澱積依製程的細節可能 需要3〜10個澱積循環。科學文獻中使用例如“位阻（steric hindrance) 一詞來描述在一個澱積循環產生此種副單層被覆 (SUb_m〇n〇layer coverage)的機制。但亦有因其他理由在每一澱積 循％後無法獲得完整的單層澱積被覆物。此一情況留有在步驟 c)前使用有機金屬化學品處理該初步澱積物而在該初步澱積物 上澱積附加材料之可能性’假使步驟c)之有機金屬化學品可以與 該材料（初步澱積物）至少部分的反應（例如藉實行，可能是藉 反覆實行步驟a)及b))。 曰 為了從該澱積物形成具有上述之有利性質之導電性氧化 膜，可在澱積表面交替形成初步澱積物，並藉有機金屬化學品處 ，數次。在圖1及圖2所示之本發明實施例中，上述加工處理係 藉反覆實行澱積循環1或數次’即實行該循環2或更多次而完成。 依上述本發明實施例形成與基體2的形狀相一致（吻之 導電性氧化膜1。此在圖3示意性的顯示，其中基體2係置〇於反 應室中使該基體2靠在反應室之牆面3。該殿積層（即氧化膜） 1依其厚度亦呈暗灰色調。如圖3所示，反應室之牆面3遮蓋基 體2之-部分，因此薄膜丨無法在難遮蓋部分4成長。亦可^ ，體2的其他部分機械的遮蓋使在基體2的選定部分殿積薄膜 藉適當選用化學品及加工參數澱積薄膜丨，可使擔負薄膜 長之吸附反應發揮自限特性，進而改進薄们之吻合性及均勾 16 201132788 性。下舉之實施例將詳細說明在基體2上成長薄膜1之方法。 <實施例1 > 本發明第一實施例（參照圖1)係使用不同加工溫度在基體 上形成導電性氧化膜。首先於P400 ALD分批裝置（芬蘭Beneq 公司製售）之反應室中放置厚度0.3毫米（mm)之視覺上大致透明 之D263T玻璃基體（德國scholt公司製售）。該基體為平板狀， 俾能作可信賴之透光測定。將此基體置於反應室内，使其玻璃底 部側全被遮覆使只能在其曝露於反應室圍氛之頂面成長（形成） 薄膜。在此實施例中作為上述載送氣體及用以沖淨反應室之氣體 為氮1氣(N2)。 於基體運送至ALD裝置後，將反應室抽排至減壓狀態，繼 之連續的引入載送氣體於該反應室，使其上昇至約1毫巴（1 hpa) 之加工壓力，然後加熱基體至加工溫度。反應室内之溫度係藉電 腦控制於加工溫度歷時4〜6小時。 待到達加工溫度及使該溫度隱定化後，將處理步驟1)進至 第一曝露步驟a)(參照圖1)。脈衝工序a)、b)、c)係實行一次， 然後在處理終了及從ALD裝置之反應室取出基體前又反覆實行 499 次。 使基體表面曝露於特定之化學品係藉調節p4〇〇ALD裝置之 脈衝閥（pulsing valve)控制流入反應室中之先驅物化學品來實 施。反應室之沖淨則藉關閉脈衝閥控制流入反應室中之先驅物化 學品而只讓載運氣體連續流過反應室來實施。 此實施例之脈衝程序（pulsing sequence)的詳細如下： 曝露於Η20 0.6秒、沖淨1·5秒、曝露於TiCl4 0.4秒、沖淨 17 201132788 2主〇秒、、曝露於三輸呂0.5秒、沖淨2 〇秒。在此程序之曝露 時間及冲淨時間分別指—特定化學^ ^ 竹疋化于°°之一特定脈衝閥保持開放 (〇_的時間及所有之化學品用脈衝_持關_時間。 由於形成㈣膜之絲性能或電磁衰減性能，依電磁場基本 ，、理，係與導電性薄膜有關連，因此對於在m 及现 ^等不同加工溫度形成之導電性氧化膜，藉測定通過基體玻璃 (此基體之-側面形成有導電性氧化膜）之光傳輸 transmission)評估，其結果如圖4所示。 由圖4所示可知’在23(TC、28〇t及3贼成長之導電性氧 化膜之電磁光譜的可視部分4〇〇〜75〇nm顯示相當均勻之光吸收 性，同時該導電性氧化膜亦具可視之暗灰色。 >達成本實施例之薄膜成長的吸附反應機制雖然、尚未明晰，但 試驗顯示該化學吸附反應為某程度係自限式（即自調節）的。此 導致在基體表面、‘甚至複雜之非平坦表面上形成極為吻合 (conformal)且均勻之薄膜。 此種薄膜（導電性氧化膜）厚度的測定極為困難，因為接收 使用光學或偏振光橢圓計測之結果並不容易。正確的測值可使用 TEM,或HRTEM法獲得，但極為昂貴，在較低溫度下形成之薄 膜之歲積速度為約〇 llnm/cycle.e在較高溫度下形成薄膜之澱積 速度可能不相同，但形成之膜厚約為55nm。依據導電性測定， 形成之薄膜具有導電性（參照圖4 ) » <實施例2 > 依本發明之第2實施例，在基體上形成導電性氧化膜（如g 2所不）。首先將厚度〇.3mm之目視上大致透明之D263T破璃3 18 201132788 體（德國Schott公司製售）置於P400 ALD裝置（芬蘭Beneq公 司製售）之反應室。此基體為平板狀，可作可信賴之光傳輸測定。 該基體係以其一側面曝露於反應室環境而另一側面被遮覆之狀 態放置於反應室中。在此實施例中上面所述之載運氧體及用以沖 淨反應室之氣體為氮氣(N2)。 準備將基體載送至ALD裝置之後，將該裝置之反應室抽排 至減壓狀態，然後連續引入載送氣體使反應室達到加工壓力（約 lmbar)，隨後將該基體加熱至280°C之加工溫度，並藉電腦將反 應室之溫度穩定的控制於加工溫度，歷時4〜6小時。 待到達加工溫度及穩定化後，如圖2所示，開始從步驟〇 進到第1曝露步驟a)。首先將脈衝程序即步驟a)、b)、c)，然後 再度b)實行-次，然後在製程結束*從AU)裝置之反應室取出 基體前將上述各步驟反覆實行1999次。 使基體表面曝露於特定之化學品係藉調節剛ALD裝置之 脈衝閥控制流人反應室中之Μ物化學品來實施。反應室之沖淨 則藉關閉脈衝f雜制流人反應室中之先驅物化學品而只載運氣 體連續流過反應室來實施。 此實施例之脈衝程序的詳細如下： 曝路於H2O 0· 6秒、沖每1 ς 丨 π 邝/尹h5秒、曝露於TiCl4 0.4秒 '沖淨 2,〇秒、曝露於三甲基銘0.5秒、沖淨2m少。在此程序 時間及沖淨時間分別指一特定化風〇 、 ^ ^ M R ^ 哥疋化予〇〇之一特定脈衝閥保持開放 的時間及^有之化學品用脈衝閥保持_的時間。 Π成之導電性氧化膜亦同樣藉測定兩側面形成 璃基體（圖5中之樣品⑼）的光透射率（〇pUcal 19 201132788 transmission)評價。圖5中之數據表示測定結果。此圖亦表示與 本發明第1實施例形式之導電性氧化膜的傳送數據的比較。此薄 膜亦依實施例的相同程序在加工溫度28(rc所形成者，其不同之 處為其步驟a)、b)、c)僅先實行1次繼之反覆1999次。 由圖5可知’兩種導電性氧化膜在電磁光譜之可視的 400〜750nm部分顯示相當均勻之光吸收性。 雖然此實施例中之薄膜成長的吸附反應機制尚未完全明 晰，但試驗結果顯示化學吸附反應某程度係自限式 (sef-limiting^此可以使基體表面，甚至非平坦表面之廣大部份 形成極為均勻的保形膜。此氧化膜（樣品191)的厚度為約22〇nm 而且依據導電性測定值（依實施例4測定），此氧化膜為導電性。 <實施例3 > 圖6所示傳輸資料（數據）係獲自實施例】之導電性氧化膜 (即圖6之樣品191 )。此氧化膜係依實施例丨之相同程序在溫 度280°C下形成者，所不同之處為程序（步驟）a)、b)、c)僅 實行1次，然後反覆1999次。 由圖6可知，此薄膜在電磁光譜之可視的4〇〇〜75〇nm部分 顯示相當均勻之光吸收性。 雖然此實施例中之薄膜成長的吸附反應機制尚未完全明 晰，但試驗結果顯示化學吸附反應某程度係自限。此可以使基體 表面，甚至非平坦表面之廣大部份形成極為均勻的保形膜。此氧 化膜（樣品191)的厚度為約220nm而且依據導電性測定值（依 實施例4測定），此氧化膜為導電性。 20 201132788 <實施例4 > 使用FLUKE 8060A多用途計量器從探頭距離10mm處測定 由本發明不同實施例所形成之數種氧化膜的導電性。此種測定方 法之詳細為精於此項技術人所熟知。下表1顯示測定結果，表中 以mohm表示電阻(resistance)，其目的在依此數值判定形成之薄 膜是絕緣性抑或導電性。此等性質乃取決於實際所測之膜厚。 表1 :依本發明實施例方法形成之氧化膜的導電性資料 樣品 薄 膜 加工溫度(°C) 膜厚(nm) 電阻(mohm) 185 500* (H20+TiCl4+TMA) 330 about 55 nm 73 186 500* (H20+TiCl4+TMA) 280 about 55 nm 36 187 500* (H20+TiCl4+TMA) 230 about 55 nm 100 190 2000* (H20+TiCl4+TMA) 230 about 220 nm 23 191 2000* (H20+TiCl4+TMA) 280 about 220 nm 10 196 2000* (H2〇+TiCl4+TMA +TiCl4) 280 - 0, 59 194 2000* (2* (H20+TiCl4+ TMA+TiCU) 280 - 3, 1 195 667* (3* (H20+TiCl4)+ TMA) 280 - 1,8 由上表所示結果可知，依本發明方法形成之氧化膜皆為導電 性。 <生成之組成物> 使用SEM-EDS (掃描電子顯微鏡-電子色散分光計）技術測 定依本發明之不同實施例形成之數種導電性氧化膜之元素組 成。此種技術之詳細為精於此項技術之人所熟悉。圖7表示此種ZnO: AI and In2〇3: Transparent conductive oxides such as Sn (TC〇) were previously used in the ALD method. However, even if these oxide films are electrically conductive, they are substantially transparent in the visible wavelength range. A method of forming a coating layer with a dark coating is disclosed in U.S. Patent No. 7,270,895. The method of forming a coating layer is cathode arc evaporation (CAE), sputtering, and PVD. A common problem with these coating methods is that uniform coating cannot be achieved for complex shaped substrates and non-planar surfaces. This is particularly problematic in decorative applications because the coating layer required is to evenly coat the entire surface of the substrate. The oxidative complex (〇2〇3) is a commonly known material that exhibits a dark gray tone. Therefore, it has been widely used, and the deposition method of the chromium oxide is disclosed in the method of depositing chromium oxide in the U.S. Patent No. 7,147,794 on a non-flat surface such as a three-dimensional (3D) object of a complicated shape to form a uniform thickness. Covered film. At the same time, chromium and oxidized materials have a dream. It has the problem of causing chromium allergy. 201132788 A method of forming a highly absorptive, that is, a dark-colored and electrically conductive two-dimensional (3D) object on a non-flat surface. The present inventors have encountered a need for a film material and a coating layer having a uniform thickness in various shapes. SUMMARY OF THE INVENTION An object of the present invention is to provide a novel method for opening a conductive oxide film on a base surface and to provide a novel conductive oxide film and use thereof, in order to solve the above problems of the prior art. The features of the method of the present invention are defined in the claims section of the patent application; the conductive oxide film produced in this month is defined in claim 19 and the use of the oxide film is defined in claims 26 and 27. The method of the present invention for forming a conductive oxide film on a surface of a substrate comprises the steps of: placing a substrate in a reaction t; forming a preliminary coating on a depose surface of the substrate; and using a chemical ( The precursor material is to deposit the surface of the plating layer. The above step of depositing the preliminary plating on the surface of the substrate includes: removing the preliminary plating of the transition metal oxide on the deposition surface except the 'cleaning reaction chamber; The step of treating the surface of the forged layer includes: treating the surface of the coating with an organometallic chemical, the organometallic chemical containing a first metal such that at least a portion of the organic chemical can react with the preliminary plating, followed by blowing Clearing the reaction chamber to form an oxide containing oxygen, a first metal, and a transition metal; the step of forming a preliminary plating layer and treating the surface of the plating is performed alternately to form a conductive oxide thin layer on the surface of the substrate ( That is, the oxide film). The conductive oxide of the present invention contains oxygen, a first metal, and a transition metal. The oxygen 201132788 film is deposited by a substrate ( Forming a preliminary deposit of a transition metal oxide on the surface, followed by blowing to remove the reaction chamber, and then treating the deposited surface with an organometallic chemical containing a first metal to at least a portion of the organic chemical At least a portion of the preliminary bonding layer is reacted, and then the reaction chamber is purged to form an oxide containing oxygen, a first metal, and a transition metal. The steps of forming the preliminary plating layer and treating the deposition surface are alternately repeated until the substrate is A conductive oxide film is formed thereon. It should be noted herein that the term "conductivity" as used herein means that the film is electrically non-insulating, that is, unless otherwise noted, the term includes semiconductive and electrically conductive films. The term "deposit" means a very small amount of material (7) to strike (4), for example, a coating having a thickness less than a few atomic layers (m〇n〇hyers), where the atoms may not be grouped into a specific phase ( The advantages of the present invention are exerted. It has been found that the step of forming a preliminary deposition and the step of treating the deposited surface with an organic chemical are repeated: T exerts a conductive oxidation on the surface of the substrate to enable the material to have beneficial properties. For this reason, "film", the word library is solved as a Π = the amount of material is sufficient for the atomic group in the film to be in the phase to have and " = the step in the text "forms preliminary _" It must be carried out continuously, and in accordance with the invention, there may be some other steps between. These other steps may include, for example, the order that he should not finish the growth of the house, so that the preliminary house and the organometallic chemicals i are reversed, and the steps of the m-knife step = the accumulation of the product The overlap of the alternating March. This means that in the same reaction room, there will be no 201132788 = a large amount of initial accumulation of all chemicals and the treatment of the surface of the house = the dry product (organometallic chemicals) exists here, the initial area The formation process does not significantly affect the processing of the deposited surface, and vice versa, but those who are skilled in this secret can know according to the disclosure of this specification, when the above two steps are, for example, the same, should be implemented in the room, The residual chemicals of the step may remain in the reaction chamber for a long period of time, and this residue may affect the subsequent processing steps to some extent, i.e., the two steps overlap in time. Thus, the two steps are alternately carried out = : The shape of the tube is controlled, and the chemical reaction of the film mainly occurs on the surface of the temple = not in the gas phase of the surface of the far n. Unless otherwise stated, this definition is also subject to the other processing steps outlined in this specification. According to a first embodiment of the present invention, the preliminary structure of the transition metal oxide includes, in any order, an alternating step: a) the exposed surface of the exposed substrate is at least containing the oxidation time/吏4 oxygenated chemical A portion is adsorbed onto the deposition surface and subsequently flushed to the reaction chamber; b) the deposited surface of the exposed substrate is adsorbed onto the deposition surface at least one point of the transition metal chemical, and then the reaction chamber is flushed. According to a second embodiment of the present invention, the step of treating the deposited surface using the organometallic chemical comprises: c) exposing the deposited surface of the substrate to the organometallic chemical such that at least a portion of the organometallic chemical is adsorbed to the On the surface of the deposition, follow the reaction chamber. Further, in accordance with an embodiment of the present invention, the method of the present invention forms conductive yttria on a substrate for absorbing light. The method of the present invention according to another embodiment is for forming a conductive bismuth film on the substrate to attenuate electromagnetic waves propagating in the conductive oxide film in a visible wavelength range. According to an embodiment of the present invention, a conductive oxide film is used as a coating of a substrate, 201132788 is used to absorb light, and according to another embodiment, a conductive film is used as a substrate to attenuate electromagnetic waves in the conductive oxide film. It is transmitted in the visible wavelength range. The term "visible wavelength range", unless otherwise noted, is as if a human can see a wavelength band 'that refers to the side of the electromagnetic spectrum ~ 75 nanometers (nm) wavelength band 0 film according to the invention - embodiment The method comprises forming a conductive light absorbing oxide π. The method comprises forming a high loss film (1 〇 ssy fUm). In addition, according to the hairpin method, even if the surface of the three-dimensional (3D) object is a complex non-flat surface, an extremely fine coating film can be formed, and the method of the present invention contributes to, for example, the use of the coated sugar as an optical device. The material of the coating film has good chemical stability, that is, for example, when the hair is exposed to atmospheric conditions or other potential oxidizing conditions (in which case the film body may be exposed to moisture, and/or oxygen), the stability is good. . Further, the method of the present invention can produce a conductive oxide film which can accurately control the conductivity of the film. The materials forming the film are also surprisingly having a high absorption coefficient, and some materials have a fairly uniform absorption spectrum in the visible portion of the electromagnetic spectrum (abs〇rpti〇n (4). The theoretical basis for the method of the present invention It can be considered as: when the first (metal) metal oxides and the organic metal, the first metal of the school is incorporated into the crucible as one of them: optically absorptive conductive oxide. About 70% (including gas, I5,, ..." visible light and conductive oxide visible light and Qinglang oxide; phase provides a high absorption coefficient of such a conductive oxide film (ie, oxide conductive film) can be alternated with preliminary temples and Formed by the step of treating the material. The conductive oxide 2 8 201132788 has the advantage. In addition, the repeated execution of the above steps results in at least part of the phase control to make the conductive film of the shape of the conductive film - aity) A profile having a fairly uniform thickness. There are many steps in the steps of the embodiments of the present invention and c). Some embodiments have a specific order. That is, some embodiments a) and eclipse i through m 彡 初步 初步 四 四 四 四 四 四 四 四 四 四 四 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步 初步Steps a), b) and c) are repeated in the order of a), b), c) and then - or increase the film thickness multiple times. There is also a f ^ 彳丨 V a), ^ * And c) repeat the sequence one or more times in the order of a), b), c) to increase the film thickness. Further, the __ embodiment, steps a), b) and c) a) and b) and repeating the steps one or several times after the step is performed. Since each time the surface of the substrate is exposed to the chemical, a part of the chemical is adsorbed on the surface of the substrate. Therefore, in some embodiments of the present invention, the thickness of the deposited film can be controlled by the number of times the surface of the substrate is exposed to the chemical. The method of forming a film on the substrate can control the thickness of the film very accurately, and thus the film The total absorbance, which is the darkness of the film, can be properly controlled. When the chemical that acts as a film grows alternately in the reaction chamber, the chemical is It can be fully mixed, and the formation of the highly absorbing film is mainly controlled by the adsorption reaction of the deposition surface. The kinetics of these adsorption reactions are mainly controlled by the properties of the deposition surface, which is less affected. The effect of the flow kinetics of the chemical on the surface of the deposition chamber within the reaction chamber, but in some embodiments of the invention, it results in a highly conformal and uniform thickness of the deposited surface of the substrate of any shape. According to an embodiment of the present invention, steps a), b) and c) are each performed one or several times to form a film having a thickness of 1 nm to 2 μm on the substrate. When the film thickness is below 1 nm or 2 μm Above the film, the film is visually transparent and opaque, respectively. Therefore, a film having a thickness between the above 1 nm and 2 μm can be effectively used as a gray scale filter. According to one embodiment of the invention, the pressure in the reaction chamber is maintained between 0.1 mbar (O.lhpa) and 100 mbar (lOOhpa) when the surface of the substrate is exposed to the chemical. According to another embodiment, the surface temperature of the substrate is in the range of 150 ° C to 600 ° C, preferably in the range of 200 ° C to 500 ° C, preferably in the range of 250 ° C to 450 ° C. According to an embodiment of the invention, the transition metal chemical is a transition metal il. According to another embodiment, the transition metal halide is a transition metal chloride, and according to still another embodiment, the transition metal vapor is selected from the group consisting of: titanium trioxide, titanium tetra-titanate, gasification of four gases, Four gasification sputum, five gasification sharp, five gasification group, five gasification turn and six gasification crane. According to another embodiment of the invention, the transition metal chemical is an ethanol compound containing a transition metal. According to an embodiment of the invention, the metal portion of the organometallic chemical is selected from the group consisting of aluminum, gallium and transition metals. According to one embodiment of the invention, the organic portion of the organometallic chemical contains an alkyl ligand, and according to another embodiment, the organometallic chemical is tridecyl aluminum. According to an embodiment of the invention, the oxygen containing chemical also contains hydrogen. Another embodiment of the oxygenated chemical is water. According to other embodiments, the oxygenated chemical is ozone, oxygen ions, oxygen, ethoxylated metal, H202, and N2. By the appropriate selection of chemicals and processing parameters, especially the substrate temperature when the substrate surface is exposed to chemicals and the pressure in the reaction chamber, the deposition of the surface of the adsorbed chemical on 10 201132788 and the preliminary deposition of the transition metal oxide and The action of treating this preliminary deposit with an organometallic chemical becomes self-limiting. This further improves the uniformity of the uniformity of the film thickness and the conformality of the surface of the solid object having a complicated shape. Additionally, the chemicals listed above are inexpensive and the process of the invention can be practiced at low cost. According to an embodiment of the invention, the substrate is non-planar. Further, in accordance with an embodiment of the present invention, the film preferably contains oxygen in the range of 40 to 80% by atom, preferably 55 to 75 atom%, most preferably 60 to 70 atom%. According to another embodiment of the invention, the film preferably contains a first metal in the range of 5 to 40% by atom, preferably 7 to 30 atoms. /〇, preferably in the range of 10 to 25 atom%. Further, according to still another embodiment of the present invention, the film preferably contains 6 to 30 atom% of a transition metal, preferably 10 to 25 atoms/. It is preferably in the range of 13 to 23 atom%. The film of the present invention contains oxygen, a transition metal and a first metal, and the ratio of the atom of oxygen to the atomic % of the transition metal and the atomic % of the first metal is in the range of 1.8 to 2.1. The advantages of the present invention are further highlighted by the composition range described above. According to an embodiment of the invention, the first metal is aluminum, and in another embodiment the transition metal is titanium. According to an embodiment of the invention, the oxygenated chemical is water, the transition metal chemical is titanium tetrachloride and the organometallic chemical is triterpene I. According to an embodiment of the invention, the substrate is substantially transparent in the visible portion of the electromagnetic spectrum. According to another embodiment, the substrate is a lens. The film of the present invention can be used on lenses such as glasses to have a special color appearance while reducing the color appearance to maintain a natural visual effect. The embodiments of the invention described above can be used in any combination. Several real-world 11 201132788 configurations can be combined to form another embodiment. Further, the method, product or use of the present invention may comprise at least one of the above-described embodiments of the present invention. [Embodiment] Several embodiments of the present invention will be described below with reference to the drawings. </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; For example, the construction of a processing apparatus suitable for carrying out the methods of the following embodiments of the present invention is known to those skilled in the art in light of the disclosure herein. The apparatus can be, for example, an ALD (Atomic Layer Deposition) apparatus conventionally suitable for processing the following chemicals. ALD devices (i.e., reactors) are disclosed in U.S. Pat. In connection with the operation, for example, the substrate is introduced into the reactor, the reaction chamber is evacuated to a low pressure, or if the treatment is carried out under atmospheric pressure, the flow rate of the gas flowing into the device is adjusted, and the substrate and the reaction chamber are heated. Those who are skilled in this technology can be easily identified according to this specification. In addition, many other operations and features are not described or described in detail in order to highlight the features of the various embodiments of the invention. In the present specification, the terms "substrate surface", "surface" and deposited surface ', unless otherwise specified, are used to refer to the surface of the substrate or the surface of the film which has been formed on the substrate. The change occurs during the method in which the deposition surface forms a film by adsorbing chemicals on the surface of the substrate. The following embodiments of the invention are initiated by placing the substrate in a reaction chamber such as a typical reaction apparatus to which the ALd method is applied (step 丨), which is then pumped down by vacuum or the like to form a film. The pressure, or if a 12 201132788 atmospheric ALD device and/or method is used, is typically provided with a gas stream from the atmosphere to protect the deposition zone. The base body can be introduced into the reaction chamber, for example, by a hermetic load lock device or simply by a loading hatch. The substrate may be heated by a resistance heating element or the like, which involves the entire reaction chamber. The above step 1) may also include other preparation procedures such as growing a film on a substrate or preparing a substrate for a subsequent processing step. This preparation procedure can be determined depending on the reaction apparatus or the operating environment of the reaction apparatus. The implementation of such procedures is apparent to those skilled in the art in light of this description. After the substrate and reaction chamber have reached a predetermined temperature and conditions suitable for deposition, the deposition surface is alternately exposed to different chemicals to form a preliminary deposition of the transition metal oxide. Such preliminary deposition may be formed in other embodiments of the invention by methods such as CVD or PVD, which do not alternately expose the deposited surface to different chemicals. The surface of the substrate should be exposed to gaseous chemicals. That is, the chemicals are first placed in a container, heated or not heated according to the nature of the chemical, vaporized, and then the vaporized chemical is quantitatively introduced into the reaction chamber through a conduit of the reaction device. This quantitative introduction of vaporized chemicals can be carried out by means of a valve installed in a pipe, which is commonly referred to as a pulsing valve in a suitable ALD device. Other mechanisms for contacting the substrate with the chemical in the reaction chamber are also conceivable, one of which is to move the surface of the substrate within the reaction chamber (to move in place of the vaporization chemical), even if the substrate passes through the area occupied by the vaporous chemical. A typical ALD reactor also contains facilities for flushing residual chemicals and reaction by-products into a reaction chamber prior to directing another chemical into the reaction chamber. This feature, along with the quantitative introduction of controlled vaporization chemicals, allows the substrate surface to be alternately exposed to chemicals, eliminating the need to over-mix different chemicals in the reaction chamber and other parts of the ALD reactor. In practice, the carrier gas (tetra) gas is typically continuously passed through the reaction chamber during the deposition process and a variety of chemicals are introduced into the reaction chamber along with the carrier gas. Purgmg of the reaction chamber does not require complete removal of the remaining chemicals and reaction by-products from the reaction chamber, often allowing the presence of residues of these or other materials. Following the process step U discussed above, step a) is carried out in accordance with the first embodiment of the invention (as shown in the figure), that is, the surface of the substrate is exposed to an oxygen-containing chemical. After such treatment, under the appropriate processing conditions discussed above, the a-oxidized ac of the adsorbed portion of the surface may be exposed to the transition metal chemical (step b) after flushing the reaction chamber. A portion of the transition metal chemical can be formed by the step formation = surface adsorption. In step b) after step a), a preliminary deposit of transition metal oxide is formed on the surface of the temple. After the rinsing step of step b), the formed surface is exposed to an organometallic chemical (step c)), i.e., the primary granule is treated with an organometallic chemical. After this treatment, the portion of the metallurgical chemical adsorbed on the surface of the surface can cause the first metal in the organometallic chemical to enter the house. The iW is flushed to the reaction chamber. As described above, each of the exposure steps a), 匕) or 0 can form an additional deposit on the surface of the _ as a result of the adsorption reaction of the corresponding chemical and the surface of the temple. The thickness of the line on the substrate can be increased by repeating steps a), b) and c) in sequence, as shown in the flow chart. When the deposit is of sufficient thickness, the deposit forms a thin film of a thin conductive oxide material composed of oxygen, an oxide material from a film, a first metal of a product, and a transition metal. The advantage described above 2 is to stop the alternate exposure treatment after the film thickness of the target is reached, and the processing procedure is terminated. 14 201132788 According to a second embodiment of the present invention, step a) is to expose the surface of the substrate to oxygen-containing material, as indicated by circle 2. The surface of the oxygen-containing chemical is adsorbed to the surface of the substrate by exposing the surface to the s-oxygen chemical under appropriate processing conditions as described below. After the reaction has been flushed, the surface is exposed to a transition metal chemical (step b)), and a portion of the transition metal chemical is adsorbed onto the surface formed by the step & A preliminary deposit of a transition metal oxide can be formed on the deposition surface in step a). ^ After the step b) is rinsed, the formed surface is exposed to organometallic chemicals :)) The preliminary deposit is treated with organometallic chemicals. This treatment can adsorb a portion of the organometallic chemical at the surface = as a result of which the first metal of the organometallic chemical is incorporated into the deposit. The reaction chamber is then flushed, and the resulting surface is again exposed to the transition metal chemicals, which are then flushed to the reaction chamber, i.e., step b) is repeated. As described above, as a result of the adsorption of the corresponding chemical and the deposition surface, each exposure (4) a), _e) can form an additional temple on the surface. The thickness of the temple deposits on the substrate can be increased by repeating the steps a), b)^c) and b) in the order shown in FIG. When the deposit reaches a sufficient thickness, the temple is shaped as an oxygen, a metal from an organometallic chemical, and an oxide of a transition metal. _ Conductive oxide film has the above discussed? The nature of wealth. Stop the alternate exposure and terminate the process when the target film thickness is reached. Balance 2 is the minimum repeating procedure for the exposure step, which is called “pulse ^r^(p lsingsew ;ffl b), c), and the pulse program of the second embodiment of FIG. 2 a), thief = in the chemical department Different chemicals may be used in each exposure step of the process. For example, & diagram/the first-real_, the oxygen-containing chemicals of step a) may be changed repeatedly according to each pulse program b), e). Suitable for other embodiments. 15 201132788 The above method may not provide a complete single layer deposited film in a deposition cycle. After each deposition cycle, the deposition surface has many open micleation sites. A complete single layer deposition may require 3 to 10 deposition cycles depending on the details of the process. For example, the term "steric hindrance" is used in the scientific literature to describe the generation of such a sub-monolayer coating in a deposition cycle. (SUb_m〇n〇layer coverage) mechanism. However, for other reasons, a complete single-layer deposition coating cannot be obtained after each deposition cycle. This condition leaves the possibility of treating the preliminary deposit with an organometallic chemical prior to step c) to deposit additional material on the preliminary deposit 'provided that the organometallic chemical of step c) can be used with the material (Preliminary deposits) at least part of the reaction (for example, by implementation, may be carried out by repeating steps a) and b)).曰 In order to form a conductive oxide film having the above-described advantageous properties from the deposit, a preliminary deposit may be alternately formed on the deposition surface, and the organometallic chemical may be used several times. In the embodiment of the invention shown in Figs. 1 and 2, the above-described processing is carried out by repeatedly performing a deposition cycle 1 or several times, i.e., performing the cycle 2 or more times. According to the embodiment of the present invention described above, the shape of the substrate 2 is formed (the conductive oxide film 1 of the kiss. This is schematically shown in Fig. 3, wherein the substrate 2 is placed in the reaction chamber so that the substrate 2 is placed in the reaction chamber. Wall 3. The hall layer (ie, oxide film) 1 is also dark gray in color according to its thickness. As shown in Figure 3, the wall 3 of the reaction chamber covers the portion of the substrate 2, so the film can not be covered in the difficult part. 4 growth. Also ^, other parts of the body 2 mechanical cover so that the selected part of the substrate 2 deposited film by appropriate selection of chemicals and processing parameters deposited film 丨, can take on the long-term adsorption reaction of the film to play self-limiting characteristics Further improving the conformity of the thinner and the uniformity of the thin film. The following embodiment will explain in detail the method of growing the thin film 1 on the substrate 2. <Example 1> First embodiment of the present invention (refer to Fig. 1) A conductive oxide film is formed on the substrate using different processing temperatures. First, a visually substantially transparent D263T glass substrate having a thickness of 0.3 mm (mm) is placed in a reaction chamber of a P400 ALD batching device (sold by Beneq, Finland). German scholt The system is made of flat plate. The substrate can be used as a reliable light transmission measurement. The substrate is placed in the reaction chamber so that the bottom side of the glass is completely covered so that it can only be exposed to the reaction chamber. The top surface is grown (formed) as a film. In this embodiment, the carrier gas and the gas used to flush the reaction chamber are nitrogen gas (N2). After the substrate is transported to the ALD device, the reaction chamber is evacuated to minus. The pressure state, followed by continuous introduction of carrier gas into the reaction chamber, causing it to rise to a processing pressure of about 1 mbar (1 hpa), and then heating the substrate to the processing temperature. The temperature in the reaction chamber is controlled by the computer at the processing temperature. After 4 to 6 hours have elapsed. After the processing temperature is reached and the temperature is concealed, the processing step 1) is advanced to the first exposure step a) (see Fig. 1). The pulse steps a), b), and c) were carried out once, and then 499 times were repeated before the end of the treatment and the removal of the substrate from the reaction chamber of the ALD apparatus. Exposing the surface of the substrate to a particular chemical is carried out by controlling the precursor chemicals flowing into the reaction chamber by means of a pulsing valve that regulates the p4〇〇ALD device. The flushing of the reaction chamber is carried out by closing the pulse valve to control the precursor chemicals flowing into the reaction chamber and allowing only the carrier gas to continuously flow through the reaction chamber. The details of the pulsing sequence of this embodiment are as follows: exposure to Η20 0.6 seconds, rinsing for 1.5 seconds, exposure to TiCl4 0.4 seconds, rinsing 17 201132788 2 main leap seconds, exposure to three losers 0.5 seconds Rush 2 seconds. The exposure time and the flushing time in this procedure refer to the specific chemical ^ ^ bamboo 疋 in ° ° ° a specific pulse valve keeps open (〇 _ time and all chemicals with pulse _ hold _ time. Due to the formation (4) The silk property or electromagnetic attenuation performance of the film depends on the basic and rational magnetic field, and is related to the conductive film. Therefore, the conductive oxide film formed at different processing temperatures, such as m and current, is measured by the base glass. The light transmission transmission of the conductive oxide film formed on the side of the substrate was evaluated, and the results are shown in FIG. As shown in Fig. 4, it can be seen that the visible portion of the electromagnetic spectrum of the conductive oxide film grown at 23 (TC, 28 〇t, and 3 thieves shows a relatively uniform light absorption, and the conductive oxidation The film also has a visible dark gray color. > Although the adsorption reaction mechanism for achieving the film growth of the present embodiment is not clear, the test shows that the chemical adsorption reaction is self-limiting (i.e., self-regulating) to some extent. A very conformal and uniform film is formed on the surface of the substrate, even on complex, non-flat surfaces. The measurement of the thickness of such a film (conductive oxide film) is extremely difficult because the results of receiving optical or polarized ellipsometry are not It is easy. The correct measurement can be obtained by TEM or HRTEM method, but it is extremely expensive. The film formation speed at a lower temperature is about 〇llnm/cycle.e The deposition rate of the film is formed at a higher temperature. It may be different, but the film thickness is about 55 nm. The formed film has electrical conductivity according to the conductivity measurement (refer to Fig. 4) » <Example 2 > According to the second embodiment of the present invention, A conductive oxide film (such as g 2) is formed thereon. First, a visually substantially transparent D263T glass 3 18 201132788 (sold by Schott, Germany) is placed in a P400 ALD device (manufactured by Beneq, Finland). The reaction chamber is sold in the form of a flat plate, which can be used for reliable optical transmission measurement. The base system is placed in the reaction chamber with one side exposed to the reaction chamber environment and the other side covered. In the embodiment, the oxygen carrier and the gas used for flushing the reaction chamber are nitrogen (N2). After the substrate is loaded to the ALD device, the reaction chamber of the device is evacuated to a reduced pressure state, and then continuously. The carrier gas is introduced to bring the reaction chamber to a processing pressure (about 1 mbar), and then the substrate is heated to a processing temperature of 280 ° C, and the temperature of the reaction chamber is stably controlled by the computer to the processing temperature for 4 to 6 hours. After reaching the processing temperature and stabilizing, as shown in FIG. 2, the process proceeds from the step to the first exposure step a). First, the pulse program, that is, steps a), b), and c), and then b) is carried out once, and then the above steps are repeatedly performed for 1999 times before the substrate is taken out from the reaction chamber of the AU) apparatus. Exposure of the surface of the substrate to a particular chemical is carried out by adjusting the sputum chemical in the reaction chamber of the pulse valve of the ALD device. The flushing of the reaction chamber is carried out by shutting off the precursor chemicals in the reaction chamber and shutting down only the carrier gas continuously flowing through the reaction chamber. The details of the pulse procedure of this embodiment are as follows: Exposure to H2O 0 · 6 seconds, rushing every 1 ς 丨 π 邝 / Yin h5 seconds, exposure to TiCl4 0.4 seconds ' rinse 2, leap seconds, exposure to trimethyl 0.5 seconds, less than 2m. In this program, the time and the flushing time refer to a specific wind, ^ ^ M R ^, the time when one of the pulse valves is kept open, and the time when the chemical is held by the pulse valve. The conductive oxide film of Fucheng was also evaluated by measuring the light transmittance (〇pUcal 19 201132788 transmission) of the glass substrate (sample (9) in Fig. 5) on both sides. The data in Fig. 5 indicates the measurement results. This figure also shows a comparison with the transfer data of the conductive oxide film of the first embodiment of the present invention. This film was also formed at the processing temperature 28 (rc formed by the same procedure of the example, except that its steps a), b), and c) were performed only once and then repeated for 1999 times. As can be seen from Fig. 5, the two conductive oxide films exhibit relatively uniform light absorption in the visible portion of the electromagnetic spectrum of 400 to 750 nm. Although the adsorption reaction mechanism of the film growth in this embodiment has not been completely clarified, the test results show that the chemisorption reaction is somewhat self-limiting (sef-limiting), which can form a large part of the surface of the substrate or even a non-flat surface. A uniform conformal film. The thickness of this oxide film (sample 191) was about 22 〇 nm and the oxide film was electrically conductive according to the conductivity measurement (measured according to Example 4). <Example 3 > The transmission data (data) shown is obtained from the conductive oxide film of the embodiment (i.e., sample 191 of Fig. 6). This oxide film is formed at the temperature of 280 ° C according to the same procedure as in Example ,, and is different. The procedure (step) a), b), c) is performed only once, and then repeated 1999 times. As can be seen from Fig. 6, the film exhibits a relatively uniform light absorption in the visible portion of the electromagnetic spectrum of 4 〇〇 to 75 〇 nm. Although the adsorption reaction mechanism of the film growth in this embodiment has not been fully clarified, the test results show that the chemisorption reaction is self-limiting to some extent. This allows a very uniform conformal film to be formed over a large portion of the surface of the substrate, even the non-flat surface. The thickness of this oxide film (sample 191) was about 220 nm and the oxide film was electrically conductive according to the conductivity measurement (measured according to Example 4). 20 201132788 <Example 4 > The conductivity of several oxide films formed by different embodiments of the present invention was measured from a probe distance of 10 mm using a FLUKE 8060A multipurpose meter. The details of such assays are well known to those skilled in the art. The results of the measurement are shown in Table 1 below, and the resistance is expressed in mohm in the table, and the purpose of the film is to determine whether the formed film is insulating or conductive. These properties depend on the actual measured film thickness. Table 1: Conductivity data of oxide film formed by the method of the present invention. Film processing temperature (°C) Film thickness (nm) Resistance (mohm) 185 500* (H20+TiCl4+TMA) 330 about 55 nm 73 186 500* (H20+TiCl4+TMA) 280 about 55 nm 36 187 500* (H20+TiCl4+TMA) 230 about 55 nm 100 190 2000* (H20+TiCl4+TMA) 230 about 220 nm 23 191 2000* (H20+ TiCl4+TMA) 280 about 220 nm 10 196 2000* (H2〇+TiCl4+TMA +TiCl4) 280 - 0, 59 194 2000* (2* (H20+TiCl4+ TMA+TiCU) 280 - 3, 1 195 667* ( 3* (H20+TiCl4)+ TMA) 280 - 1,8 From the results shown in the above table, the oxide film formed by the method of the present invention is electrically conductive. <Formed composition> Using SEM-EDS (scanning) The electron microscopy-electron dispersive spectrometer technique measures the elemental composition of several conductive oxide films formed in accordance with various embodiments of the present invention. The details of such techniques are familiar to those skilled in the art. Figure 7 shows such
S 21 201132788 :疋的結果。圖中顯示依上述實施例】的方法形成之導電性 、之欽(Τι2ρ)、紹(Al2p)及氧(〇iS)的原子百分率 (此膜厚與_時間直接成比例）表示者。 、尽的函數 形成上述被測定的樣品薄膜之澱積溫度 小心)實行！次，然後反覆1999次。薄膜中之上C脈^驟 :原子濃度，表面(厚度約0 ’澱積時間1秒)除外，：氧二平5 約…及鈦約17原子%。此結果顯示:= 渡金屬⑷及第一金屬⑷，而氧的原子%與= 金屬之原子％及第-金屬之原子％之比率為約2，且為又 當純之減糾氧化物。 ’4膜為相 適當的變更製法中之步驟a)、b)及〇,可使 某範圍内調節。含有原子％之氛、1G〜25原子％之= 之t之導電性氧化膜經測定結果證明具有很好的結 -知人0視頻帶内具有高光吸收係數，以及相當好的吸收性及 冋吻5性，使這些導電性氧化膜呈高度紋收氧化物。 ^述實施财，含氧化學品為水，最好為脫離子水邮，有 $金屬化學品為三甲基紹Al2(CH3)6，但其他化學品亦可 ，=物之過渡金屬氧化物輕應之氧化鈦，而第—金屬為來自 二甲基鋁之鋁。本發明不特別限定使用上述之化 …可依據本說明書之揭示内容使用上述以外之=二 品輕易獲取本發明之利點。 雖然上面實施例揭示交替使用兩個不同化學品的脈衝 藉步驟a)及b)形成過渡金屬氧化物的初步殿積物，但 此種初頻積物可藉任何適當的方法形成，例如cvd、M〇cvd 22 201132788 或PVD法。此種初步澱積物可隨後利用含有鋁等第一金屬之有 機，屬化干。α處理而形成含有氧'第__金屬及過渡金屬之高吸收 性乳化物。對所揭示實施形態的上述修飾可由精於此項技術之人 參照本說明書實施。因此，本發明不限定於上面所舉示之諸實施 例’可在專利請求項所述範圍内加以自由地改變。 【圖式簡單說明】 圖1為本發明方法之第1實施例的流程圖。 圖2為本發明方法之第2實施例的流程圖。 圖3為顯示依本發明之一個實施例形成之薄膜如何吻合基 體的形狀之狀態。 圖4顯示本發明第1實施例所形成之薄膜的光傳輸測定資料 (數據）。 圖$顯示本發明第2實施例所形成之薄膜的光傳輸測定資料 (數據）。 圖6顯示本發明第1實施例所形成之薄膜的光傳輸測定資 料。 圖7顯示本發明第1實施例形成之薄膜之SEM-EDS組成分 析資料。 【主要元件符號說明】 1導電性氧化膜 2 基體 3牆面 4 遮蓋部分 23S 21 201132788 : The result of 疋. The graph shows the conductivity, the atomic percentage of 钦(2), 2(Al2p) and oxygen (〇iS) formed by the method of the above embodiment (the film thickness is directly proportional to _ time). The function of forming the deposition temperature of the sample film to be measured above is carefully performed) Times, then repeated 1999 times. Above the C pulse in the film: atomic concentration, except for the surface (thickness of about 0 Å deposition time of 1 second), oxygen dipenta 5 and titanium about 17 atom%. This result shows that: = the metal (4) and the first metal (4), and the ratio of the atomic % of oxygen to the atomic % of the metal and the atomic % of the metal - is about 2, and is a purely reduced oxide. The '4 film is a step (a), b) and 〇 in the appropriate modification method, and can be adjusted within a certain range. Conductive oxide film containing atomic % atmosphere, 1G to 25 atom% = t is proved to have a good knot - knowing the high optical absorption coefficient in the video band, and quite good absorption and kiss 5 These conductive oxide films are highly textured oxides. Said that the implementation of wealth, oxygenated chemicals for water, preferably for deionized water, there is a metal chemical is trimethyl sulphide Al2 (CH3) 6, but other chemicals can also, = transition metal oxides The light is titanium oxide, and the first metal is aluminum from dimethyl aluminum. The present invention is not particularly limited to the use of the above-described embodiments. The advantages of the present invention can be easily obtained by using the above-described other products in accordance with the disclosure of the present specification. Although the above examples disclose the use of pulses of two different chemicals alternately, steps a) and b) form preliminary deposits of transition metal oxides, such initial frequency products may be formed by any suitable method, such as cvd, M〇cvd 22 201132788 or PVD method. Such a preliminary deposit can then be dried using an organic machine containing a first metal such as aluminum. The α treatment forms a highly absorbent emulsion containing an oxygen 'metal' and a transition metal. The above modifications to the disclosed embodiments can be implemented by those skilled in the art with reference to the present specification. Therefore, the invention is not limited to the embodiments described above, and can be freely changed within the scope of the patent claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing a first embodiment of the method of the present invention. Figure 2 is a flow chart showing a second embodiment of the method of the present invention. Fig. 3 is a view showing a state in which a film formed according to an embodiment of the present invention is fitted to the shape of a substrate. Fig. 4 is a view showing the optical transmission measurement data (data) of the film formed in the first embodiment of the present invention. Fig. $ shows optical transmission measurement data (data) of the film formed in the second embodiment of the present invention. Fig. 6 is a view showing the optical transmission measurement data of the film formed in the first embodiment of the present invention. Fig. 7 is a view showing the SEM-EDS composition analysis data of the film formed in the first embodiment of the present invention. [Explanation of main component symbols] 1 Conductive oxide film 2 Substrate 3 Wall surface 4 Covering part 23